Compositional variations (major and trace elements) of clinopyroxene and Ti-andradite from pyroxenite, ijolite and nepheline syenite, Alnö Island, Sweden     

Jaana Hode Vuorinen  Ulf H  lenius  Martin J. Whitehouse  Joakim Mansfeld  Alasdair D.L. Skelton 《Lithos》2005,81(1-4):55-77

Clinopyroxenes from pyroxenite, ijolite and nepheline syenite from the main intrusion of the Alnö complex define two sub-parallel compositional trends with respect to Na, Ca and Fe_TOT plotted against alkali-pyroxene fractionation index (Na–Mg). Both trends define a smooth fractionation of increasing Na and Fe_TOT and decreasing Ca with increasing Na–Mg, but one set of samples contain clinopyroxenes that constantly plot at higher Na and lower Fe_TOT and Ca (at similar Na–Mg) than the rest of the samples. Clinopyroxenes with higher Ca and Fe_TOT and lower Na (trend 1) co-exist with substantial amounts of Ti-andradite (up to 70 vol.%), while the sample set defining the more Na-rich trend (trend 2) lack co-existing Ti-andradite. Clinopyroxenes from both trends show fractionated REE patterns with a distinct difference in HREE content, reflecting the content of co-existing Ti-andradite. The rocks of the first Ti-andradite-bearing trend crystallized slightly prior to the rocks of the second trend, probably from a primitive, Ca- and Ti-rich nephelinitic magma. Crystallisation of pyroxenite and melteigite occurred under low aSiO₂ and high aCaO and aTiO₂ as evidenced by the presence of perovskite and sometimes substantial amounts of magnetite. Subsequent increase in aSiO₂ is evidenced in the overgrowth of perovskite by titanite, which in turn is overgrown by Ti-andradite. Nepheline syenitic residuals crystallized under higher aSiO₂ and aNa₂O and lower aCaO and aTiO₂, which reduced Ti-andradite into an accessory phase and produced more Si- and Na-rich clinopyroxenes. Some of these residuals probably also mixed with new primitive magma producing a hybrid magma that crystallised the more Na-rich and Ca- and Fe_TOT-poor clinopyroxenes of trend 2. The complete lack of Ti-andradite in these rocks indicates different crystallisation conditions and also a different magma composition.  相似文献   

Thermally induced cation redistribution in Fe-bearing oxy-dravite and potential geothermometric implications     

Ferdinando Bosi  Henrik Skogby  Ulf Hålenius 《Contributions to Mineralogy and Petrology》2016,171(5):47

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Structural changes and valence states in the MgCr<Subscript>2</Subscript>O<Subscript>4</Subscript>–FeCr<Subscript>2</Subscript>O<Subscript>4</Subscript> solid solution series     

D.?LenazEmail author  H.?Skogby  F.?Princivalle  U.?H?lenius 《Physics and Chemistry of Minerals》2004,31(9):633-642

The influence on the structure of Fe²⁺ Mg substitution was studied in synthetic single crystals belonging to the MgCr₂O₄–FeCr₂O₄ series produced by flux growth at 900–1200 °C in controlled atmosphere. Samples were analyzed by single-crystal X-ray diffraction, electron microprobe analyses, optical absorption-, infrared- and Mössbauer spectroscopy. The Mössbauer data show that iron occurs almost exclusively as ^IVFe²⁺. Only minor Fe³⁺ (<0.005 apfu) was observed in samples with very low total Fe. Optical absorption spectra show that chromium with few exceptions is present as a trivalent cation at the octahedral site. Additional absorption bands attributable to Cr²⁺ and Cr³⁺ at the tetrahedral site are evident in spectra of end-member magnesiochromite and solid-solution crystals with low ferrous contents. Structural parameters a₀, u and T–O increase with chromite content, while the M–O bond distance remains nearly constant, with an average value equal to 1.995(1) Å corresponding to the Cr³⁺ octahedral bond distance. The ideal trend between cell parameter, T–O bond length and Fe²⁺ content (apfu) is described by the following linear relations: a₀=8.3325(5) + 0.0443(8)Fe²⁺ (Å) and T–O=1.9645(6) + 0.033(1)Fe²⁺ (Å) Consequently, Fe²⁺ and Mg tetrahedral bond lengths are equal to 1.998(1) Å and 1.965(1) Å, respectively.  相似文献   

Boron substitution in diopside evaluated through 11B nuclear reaction analysis     

U. Hålenius  P. Kristiansson  H. Skogby 《Physics and Chemistry of Minerals》2000,27(10):681-688

 Nuclear reaction analyses on boron in flux-grown Me³⁺- and Na⁺-doped diopside crystals utilising the ¹¹B(p,2α)⁴He reaction in conjunction with EMP analyses for major elements and optical absorption spectroscopy for determination of Me-valence state distributions show that appreciable amounts of B may enter the diopside lattice in crystals produced in Na₂B₄O₇ fluxes. The results indicate that the substitution ^[6]Me^3+[4]B^3+[6]Mg²⁺ ₋₁ ^[4]Si⁴⁺ ₋₁ operates in the present diopside samples in addition to the coupled substitution ^[6]Me^3+[8]Na^+[6]Mg²⁺ ₋₁ ^[8]Ca²⁺ ₋₁. The specific NRA technique applied allows for quantitative, high resolution (ca. 5 μm) B analyses at ppm level as well as high-resolution and high-contrast imaging of B-concentration patterns in minerals. The estimated detection limit and relative error of the B analyses are 10 ppm and 5–10%, respectively. Received: 20 September 1999 / Accepted: 6 June 2000  相似文献   

The MgCr2O4–MgFe2O4 solid solution series: effects of octahedrally coordinated Fe3+ on T–O bond lengths     

Davide Lenaz  Henrik Skogby  Francesco Princivalle  Ulf Hålenius 《Physics and Chemistry of Minerals》2006,33(7):465-474

The influence on the spinel structure of Fe³⁺ → Cr substitution was studied in flux-grown synthetic single crystals of the magnesiochromite–magnesioferrite (MgCr₂O₄–MgFe₂O₄) solid solution series. Samples were analysed by single-crystal X-ray diffraction, electron microprobe analyses, optical absorption and Mössbauer spectroscopy. With the exception of iron-poor samples (3–12 mol-% MgFe₂O₄), optical absorption and Mössbauer spectra show that iron occurs almost exclusively as trivalent Fe in the present samples. A very intense and broad absorption band at ca 7,800 cm^?1 dominates the optical absorption spectra of samples with higher Fe-contents. The appearance of this band is related to a distinct structural disorder of Fe³⁺ and a development of magnetic ordering as demonstrated by Mössbauer spectra. Profound composition-related changes are observed in the Mössbauer spectra, which are magnetically unsplit in the range 2–41 mol-% magnesioferrite, but become magnetically split in the range 59–100 mol-% magnesioferrite. Structural parameters a ₀ and M–O increase with magnesioferrite content and inversion degree, while u and T–O decrease. Our study confirms the previously reported (Lavina et al. 2002) influence of Fe³⁺ at the M site on T–O bond lengths in the spinel structure.  相似文献   

Coordination of boron in nominally boron-free rock forming silicates: Evidence for incorporation of BO₃ groups in clinopyroxene   总被引：1，自引：0，他引：1  

Ulf Hålenius  Henrik Skogby  Sabrina Nazzareni  Jeppa Resmark 《Geochimica et cosmochimica acta》2010,74(19):5672-1594

To explore mechanisms of B-incorporation in common chain silicates we have investigated synthetic diopside samples produced under boron-saturated conditions by ¹¹B and ²⁹Si magic-angle spinning (MAS) NMR and single-crystal NRA, FTIR, EMP and XRD/SREF techniques. Our samples contain 0.14-0.65 wt.% B₂O₃. NMR reveals that B is predominantly present in trigonal coordination in the clinopyroxene structure. This observation is supported by vibrational bands characteristic for B-O stretching in BO₃ groups in the range 1250-1400 cm⁻¹ in polarised single crystal FTIR-spectra. Single crystal structure refinements suggest that boron replaces Si at the T site. Combined, these results suggest that boron replacement for Si at the T-site leads to disruption of one of the T-O bonds of the nominal clinopyroxene structure resulting in replacement of SiO₄ tetrahedra by BO₃ groups. Our results show that high concentrations of boron can be incorporated in the nominally boron-free diopside. Elevated B-concentrations in the present calcic clinopyroxenes are accompanied by modifications of the diopside crystal structure involving the breaking of one T-O bond and simultaneous formation of vacancies at the octahedral M2 site. These structural modifications destabilize the structure and constitute thereby limiting factors for incorporating higher boron concentrations in diopside.  相似文献   

Optical Absorption Spectra of (Mg,Fe)SiO3 Silicate Perovskites     

Guoyin Shen  Yingwei Fei  Ulf Hålenius  Yanbin Wang 《Physics and Chemistry of Minerals》1994,20(7):478-482

Electronic absorption spectra have been measured at room temperature and pressure for polycrystalline samples of (Mg, Fe)SiO₃ silicate perovskites synthesized by multi-anvil device. One strong near-infrared band at about 7000 cm^-1 and several weak bands in the visible region were found. The near-infrared band at 7000 cm^-1 is assigned to a spin-allowed transition of Fe²⁺ at the 8–12 coordinated site in perovskite. However, definite assignments of the weak bands in the visible region are difficult because of their low intensities and the scattering effect at the gain boundaries. Crystal field calculations for Fe²⁺ at different sites in perovskite have been carried out based on the crystal structure data. The results agree with the assignment of Fe²⁺ to the 8–12 coordinated site in perovskite. Crystal field stabilization energy of Fe²⁺ with coordination number of 8 in perovskite is 3332 cm^-1 which is small compared to the octahedral site of magnesiowüstite (4320 cm^-1), another important lower-mantle mineral.  相似文献   

Low temperature spectral studies of Mn3+-bearing andalusite and epidote type minerals in the range 30000–5000 cm−1     

Smith  G.  Hålenius  U.  Langer  K. 《Physics and Chemistry of Minerals》1982,8(3):136-142

Polarized absorption spectra of natural piemontite (Ca_1.802Mn ²⁺_0.178 Mg_0.025) (Mn ³⁺_0.829 Fe ³⁺_0.346 Al_1.825) [(Si_2.992Al_0.008) O₁₂OH], viridine (Al_1.945Mn ³⁺_0.033 Fe ³⁺_0.063 Mg_0.003) [O|Si_0.970 O₄], and kanonaite (Al_1.291Mn ³⁺_0.682 Fe ³⁺_0.019 ) [O|Si_1.006 O₄] were measured at 295 and ca. 100 K. For piemontite, lowering the temperature resulted in a sharpening of broad bands in the 10 000–25 000 cm⁻¹ region supporting their assignment to single ion Mn³⁺ in M3 non-centrosymmetric sites.

Alternatively, in kanonaite, temperature behaviour pointed to a slightly stronger influence of vibronic coupling on strong bands near 16 000 and 22 000 cm⁻¹, which supported an interpretation of Mn³⁺ in nearly centrosymmetric M1 sites. Measurements at ca. 100 K show pronounced fine structure in the viridine spectra which is attributed to Fe³⁺. The ɛ values for Mn³⁺ spin-allowed bands in the three minerals lie in the range 18 to 227 [1·g-atom⁻¹·cm⁻¹].

For the same band and polarisation, ɛ values in Mn³⁺-bearing andalusite-type minerals viridine and kanonaite are the same, which indicates an absence of strong magnetic coupling effects between Mn³⁺ ions in the andalusite type structure down to ca. 100 K.

In silicates, the high ɛ values for Mn³⁺ spin-allowed bands, in comparison to those obtained for Fe²⁺ spin-allowed bands from sites of “similar distortion”, is attributed to a higher degree of covalency in the Mn³⁺-O bonds compared to the Fe²⁺-O bonds, as a result of the higher valence state of manganese.

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Spectroscopic active IVFe3+–VIFe3+ clusters in spinel–magnesioferrite solid solution crystals: a potential monitor for ordering in oxide spinels     

G. B. Andreozzi  U. Hålenius  H. Skogby 《Physics and Chemistry of Minerals》2001,28(7):435-444

Optical absorption spectra (OAS) of synthetic single crystals of the solid solution spinel sensu stricto (s.s.)–magnesioferrite, Mg(Fe³⁺Al_1???y)₂O₄ (0?y?≤ 0.3), have been measured between 12 500 and 28 500?cm^?1. Chemical composition and Fe³⁺ site distribution have been measured by electron microprobe and Mössbauer spectroscopy, respectively. Ferric iron is ordered to the tetrahedral site for samples with small magnesioferrite component, and this ordering is shown to increase with magnesioferrite component. The optical absorption spectra show a strong increase in band intensities with Fe³⁺→Al substitution. Prominent and relatively sharp absorption bands are observed at 25 300 and 21 300?cm^?1, while less intense bands occur at 22 350, 18 900, 17 900 and 15 100?cm^?1. On the basis of band energies, band intensities and the compositional effect on band intensity, as well as structural considerations, we assign the observed bands to electronic transitions in ^IVFe³⁺–^VIFe³⁺clusters. A linear relationship (R ²= 0.99) between the α_net value of the absorption band at 21 300?cm^?1 and [^IVFe³⁺]?·?[^VIFe³⁺] concentration product has been defined: α_net=2.2?+?15.8 [^IVFe³⁺]?·?[^VIFe³⁺]. Some of the samples have been heat-treated between 700 and 1000?°C to investigate the relation between Fe³⁺ ordering and absorption spectra. Increase of cation disorder with temperature is observed, which corresponds to a 4% reduction in the number of active clusters. Due to the high spatial resolution (??～?10?μm), the OAS technique may be used as a microprobe for determination of Fe³⁺ concentration or site partitioning. Potential applications of the technique include analysis of small crystals and of samples showing zonation with respect to total Fe³⁺ and/or ordering.  相似文献   

Spectroscopic studies on natural chloritoids     

Ulf Hålenius  Hans Annersten  Klaus Langer 《Physics and Chemistry of Minerals》1981,7(3):117-123

Room temperature and low temperature Mössbauer and optical absorption spectroscopic data on six natural chloritoids characterized by means of electron microprobe and X-ray powder diffraction techniques are presented. Two narrow quadrupole doublets with widths of 0.25–0.29 mm/s assigned to Fe²⁺ in a relatively large octahedral site and Fe³⁺ in a smaller octahedral site, are observed in the Mössbauer spectra. Polarized optical absorption spectra reveal three main absorption bands. A broad absorption band at 16,300 cm^?1, which is strongly polarized in E‖X and E‖Y and shows a linear increase in integral absorption with increasing [Fe²⁺] [Fe³⁺] concentration product, is assigned to a Fe²⁺+Fe³⁺→Fe³⁺+Fe²⁺ charge transfer transition. This band displays also a temperature dependence different from that of single ion d?d transitions. Two absorption bands at 10,900 cm^?1 and 8,000 cm^?1 are, on the basis of compositional dependence and energy, assigned to Fe²⁺ in the large M(1B) octahedra of the brucite-type layer in chloritoid. Combined spectroscopic evidence and structural and chemical considerations support a distribution scheme for ferrous and ferric iron which orders the Fe²⁺ ions in the M(1B) octahedra and the Fe³⁺ ions in the small M(1A) octahedral sites. Both types of octahedra are found in the brucite type layer of chloritoid.  相似文献